Method for identifying pickled Chinese cabbages in soil pit and pickled Chinese cabbages in standard pickling pool
By detecting the differential characteristic elements in the Tukeng sauerkraut and the standard pickled pond sauerkraut, establishing a discriminant model, the problem of lack of effective identification methods in the existing technology is solved, and the accurate identification of sauerkraut and the standardization of the food market is achieved.
Patent Information
- Application Number
- CN202411633308.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-14
- Publication Date
- 2025-02-14
AI Technical Summary
The existing technology lacks effective means of identifying sauerkraut and standard pickled sauerkraut, which leads to food safety issues, has an impact on the food industry, and affects the healthy development of the market.
By detecting the differential characteristic elements in the Tukeng sauerkraut and the standard pickled pond sauerkraut, establishing a discriminant model, and using orthogonal partial least squares method or classification discriminant analysis method, the two types of sauerkraut are accurately identified.
The accurate identification of sauerkraut and standard pickled pond sauerkraut is achieved. The detection cycle is short and the operation is feasible. The automatic identification success rate reaches 80%, which is of great significance to standardizing the sauerkraut market.
Smart Images
Figure CN119438362A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of food detection, and in particular to a method for identifying earth pit sauerkraut and standard pickling pool sauerkraut. Background Art
[0002] Sauerkraut is a traditional Chinese delicacy. Its original intention was to extend the shelf life of vegetables. It tastes salty and sour, is appetizing and refreshing, and is suitable for all ages. However, there is currently a lack of control over the production process. As people's living standards improve, they pay more attention to food quality and safety. It has been found that the earth cellars used for earth pit sauerkraut pose a food safety hazard. Earth pit sauerkraut is pickled on the spot after being planted. A pit is dug in the land and covered with plastic film for pickling. It is difficult to control food safety during the pickling process. At present, all earth cellars have been converted into standard pickling pools for pickling, that is, artificial square cement pools are used and epoxy resin is coated on all sides for pickling. Standard pickling pool sauerkraut has high controllability, less pollution during the production process, and is suitable for standardized large-scale production. Therefore, it is necessary to have identification technology for earth pit sauerkraut and standard pickling pool sauerkraut.
[0003] However, at present, my country still lacks effective technical means and methods for distinguishing earth pit pickled cabbage from standard pickled cabbage. The food safety problems of earth pit pickled cabbage have caused a great impact on the entire food industry and are not conducive to the healthy development of the market. Therefore, it is very urgent and important to establish a technology for distinguishing earth pit pickled cabbage from standard pickled cabbage with high accuracy, short detection cycle and wide operational feasibility. Summary of the invention
[0004] The invention provides a method for identifying earth pit sauerkraut and standard pickling pool sauerkraut. The method detects differential characteristic elements in the earth pit sauerkraut and the standard pickling pool sauerkraut, and can accurately identify the earth pit sauerkraut and the standard pickling pool sauerkraut according to the content of the differential characteristic elements, which is of great significance to standardizing the sauerkraut market.
[0005] The method for distinguishing earth pit pickled cabbage from standard pickling pool pickled cabbage provided by the present invention comprises: Obtain known earth pit sauerkraut samples and standard pickling pool sauerkraut samples from different origins; Determine the inorganic elements in the earth pit sauerkraut sample and the standard pickling pool sauerkraut sample to determine the differential characteristic elements; Establishing a discrimination model between the earth pit pickled cabbage and the standard pickled tank pickled cabbage according to the content of the differential characteristic elements; The contents of the differential characteristic elements in the sauerkraut samples to be tested are determined, and the contents of the differential characteristic elements in the sauerkraut samples to be tested are substituted into the discrimination model to distinguish between earth pit sauerkraut and standard pickling pool sauerkraut.
[0006] Optionally, the differential characteristic elements include any one or more of aluminum, arsenic, boron, barium, beryllium, bismuth, cobalt, chromium, copper, gallium, germanium, lithium, manganese, molybdenum, niobium, nickel, lead, rubidium, antimony, selenium, tin, strontium, tellurium, titanium, thallium, vanadium, zinc, and zirconium.
[0007] Optionally, the differential characteristic elements include boron, barium, copper, lithium, manganese, molybdenum, lead, rubidium, selenium, strontium, titanium and zinc.
[0008] Optionally, the analysis method adopted by the discriminant model is orthogonal partial least squares method or classification discriminant analysis.
[0009] Optionally, establishing a discrimination model between the earth pit pickled cabbage and the standard pickling tank pickled cabbage according to the content of the differential characteristic elements comprises: According to the content M of the characteristic elements boron, barium, copper, lithium, manganese, molybdenum, lead, rubidium, selenium, strontium, titanium and zinc, Y can be obtained according to the discriminant model (1) to (2). 土坑酸菜 , Y 腌渍池酸菜 Value, the Y 土坑酸菜 , Y 腌渍池酸菜 The largest value is the origin of the corresponding sauerkraut sample. The discrimination models of earth pit sauerkraut and standard pickling pool sauerkraut are: Y 土坑酸菜 =-1.3*M B +2.283*M Ba -2.32*M Cu +49.179*M Li +0.399*M Mn +31.276*M Mo +2.962*M Pb +4.076*M Rb +29.304*M Se +0.357*M Sr +3.228*M Ti +0.9*M Zn (1); Y 腌渍池酸菜 =9.045*M B -2.995*M Ba -5.504*M Cu +47.502*M Li +0.992*M Mn +47.023*M Mo -18.054*M Pb -0.004*M Rb +43.397*M Se +2.73*M Sr +0.435*M Ti -0.042*MZn (2).
[0010] Optionally, the discriminant models (1) to (2) are obtained by the following method: SPSS software was used to conduct discriminant analysis on the contents of various elements in sauerkraut samples, and Fisher's discriminant classification functions were established for earth pit sauerkraut and standard pickling pool sauerkraut, respectively, thus obtaining the discriminant models (1) to (2) mentioned above.
[0011] Optionally, obtaining known earth pit sauerkraut samples and standard pickling pool sauerkraut samples from different origins comprises: Collecting earth pit pickled cabbage and standard pickled tank pickled cabbage from multiple production areas, chopping the whole earth pit pickled cabbage and standard pickled tank pickled cabbage into small pieces and mixing them evenly, respectively obtaining uniform earth pit pickled cabbage and uniform standard pickled tank pickled cabbage; 1.0000 g of uniform earth pit pickled cabbage and uniform standard pickled pond pickled cabbage were added to a polytetrafluoroethylene digestion tank, and 4.0 mL of HNO 3 , placed in a fume hood for pre-digestion, evaporate the solution at 120°C until the yellow smoke dissipates, and add 1.0 mL of HNO 3 , 4.0mL of water, screw on the lid and put it into a microwave digestion device for digestion according to the microwave digestion program. After the digestion is completed and cooled, open the digestion tank, evaporate the solution to 1mL at 120℃, transfer the sample to a clean polyethylene plastic bottle, wash the digestion tank 3-4 times with a small amount of distilled water, combine the washing liquid in a PET bottle, dilute and fix the volume to 50.0000g, and obtain the earth pit sauerkraut sample and the standard pickling pool sauerkraut sample, respectively.
[0012] Optionally, the microwave digestion programmed temperature conditions are: 1) Raise the temperature from room temperature to 100°C and keep it for 3 minutes; 2) Raise the temperature from 100°C to 120°C and keep it for 3 minutes; 3) Raise the temperature from 120°C to 150°C and keep it for 3 minutes; 4) Raise the temperature from 150°C to 170°C and hold for 3 minutes; 5) Raise the temperature from 170°C to 190°C and hold for 15 minutes.
[0013] Optionally, the method for determining the inorganic elements is an inductively coupled plasma mass spectrometer analysis method.
[0014] Optionally, the working conditions of the inductively coupled plasma mass spectrometer analysis method include: The radio frequency power of ICP-MS analysis was 1350 W, the plasma gas flow rate was 14 L / min, the auxiliary gas flow rate was 1 L / min, the carrier gas flow rate was 0.5 L / min, the integration time was 0.1 s, and the number of mass number measurement points was 3.
[0015] The method for distinguishing earth pit pickled cabbage from standard pickled cabbage provided by the embodiment of the present invention has the following advantages compared with the prior art: The method for distinguishing earth pit sauerkraut from standard pickling pool sauerkraut of the present invention obtains known earth pit sauerkraut samples and standard pickling pool sauerkraut samples from different origins, measures the inorganic elements in the earth pit sauerkraut samples and the standard pickling pool sauerkraut samples, thereby determining differential characteristic elements, and establishing a discrimination model for the earth pit sauerkraut and the standard pickling pool sauerkraut according to the contents of the differential characteristic elements. When identifying an unknown sauerkraut sample to be tested, after measuring the contents of the differential characteristic elements in the sauerkraut sample to be tested, the contents of the differential characteristic elements in the sauerkraut sample to be tested are substituted into the discrimination model to distinguish earth pit sauerkraut from standard pickling pool sauerkraut. The method can accurately distinguish earth pit sauerkraut from different origins and standard pickling pool sauerkraut, has a wide range of operational feasibility, and a short detection cycle (10 samples can be tested within 24 hours). The automatic identification success rate of the modeling algorithm is 80%, which is of great significance for standardizing the sauerkraut market. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 The present invention is a flowchart of a method for distinguishing earth pit sauerkraut from standard pickling pool sauerkraut.
[0017] Figure 2 This is a score diagram of the orthogonal partial least squares discriminant model for earth pit sauerkraut and standard pickling pool sauerkraut established in an embodiment of the present invention, wherein the green group A is standard pickling pool sauerkraut and the blue group B is earth pit sauerkraut.
[0018] Figure 3 This is a score graph of the orthogonal partial least squares discriminant model for 10 unknown samples and pickled cabbage from pickling pools and pits in various origins in the embodiment of the present invention.
[0019] Figure 4 It is the result of SPSS classification and discriminant analysis in the embodiment of the present invention. DETAILED DESCRIPTION
[0020] As described in the background technology, at present, there is a lack of control over the production process of sauerkraut. At present, my country still lacks effective technical means and methods for distinguishing earth pit sauerkraut from standard pickling pool sauerkraut. The food safety problems of earth pit sauerkraut have caused a great impact on the entire food industry and are not conducive to the healthy development of the market. Therefore, it is very urgent and important to establish a technology for distinguishing earth pit sauerkraut from standard pickling pool sauerkraut with high accuracy, short detection cycle and wide operational feasibility.
[0021] The inventors have found through research that, based on the production characteristics of earth pit sauerkraut and standard pickling pool sauerkraut, the inorganic elements in sauerkraut are closely related to the pickling environment, and there are obvious differences between the earth pit and standard pickling pool environments. Inorganic elements are important indicators that can represent regional characteristics. Inorganic elements are ubiquitous in plants, and the inorganic elements in the soil directly or indirectly participate in the growth of plants. At the same time, during the pickling process of sauerkraut, sufficient and long-term contact with the pickling environment further leads to the accumulation and migration of inorganic elements in the pickling environment to sauerkraut. Therefore, using inorganic element content indicators to identify earth pit sauerkraut and standard pickling pool sauerkraut will have obvious characteristics.
[0022] In order to solve the above technical problems, the method for distinguishing earth pit sauerkraut from standard pickling pool sauerkraut described in the embodiment of the present invention obtains known earth pit sauerkraut samples and standard pickling pool sauerkraut samples from different origins, determines the inorganic elements in the earth pit sauerkraut samples and the standard pickling pool sauerkraut samples, thereby determining the differential characteristic elements, and establishes a discrimination model for the earth pit sauerkraut and the standard pickling pool sauerkraut according to the content of the differential characteristic elements. When identifying an unknown sauerkraut sample to be tested, after determining the content of the differential characteristic elements in the sauerkraut sample to be tested, the content of the differential characteristic elements in the sauerkraut sample to be tested is substituted into the discrimination model to distinguish earth pit sauerkraut from standard pickling pool sauerkraut. This method can accurately distinguish earth pit sauerkraut from different origins and standard pickling pool sauerkraut, has a wide range of operational feasibility, and a short detection cycle (10 samples can be tested within 24 hours). The modeling algorithm has an automatic identification success rate of 80%, which is of great significance for standardizing the sauerkraut market.
[0023] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.
[0024] The raw materials, samples, reagents, etc. used in the method for identifying earth pit pickled cabbage and standard pickled tank pickled cabbage described in the embodiment of the present invention are all commercially available products and can be purchased on the market.
[0025] The equipment used in the present invention includes: an inductively coupled plasma mass spectrometer PerkinElmer NexION 1000; a microwave digestion instrument Yiyao Technology M6; an acid removal instrument Tuojie Instrument GY-42; and an electronic analytical balance.
[0026] Please refer to Figure 1 , Figure 1 The flowchart of the method for distinguishing earth pit pickled cabbage from standard pickled cabbage in the embodiment of the present invention is as follows. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage in the present invention comprises the following steps.
[0027] S100, obtain known earth pit sauerkraut samples and standard pickling pool sauerkraut samples from different origins.
[0028] It should be noted that the earth pit pickled cabbage sample and the standard pickled tank pickled cabbage sample are both known pickled cabbage samples with determined pickled cabbage types, namely earth pit pickled cabbage or standard pickled tank pickled cabbage.
[0029] In some embodiments, the method of obtaining known earth pit sauerkraut samples and standard pickling pool sauerkraut samples from different origins includes: collecting earth pit sauerkraut and standard pickling pool sauerkraut from multiple origins, chopping the whole earth pit sauerkraut and the standard pickling pool sauerkraut and mixing them evenly to obtain uniform earth pit sauerkraut and uniform standard pickling pool sauerkraut; adding 1.0000 g of uniform earth pit sauerkraut and uniform standard pickling pool sauerkraut into a polytetrafluoroethylene digestion tank, respectively, and adding 4.0 mL of HNO 3 , placed in a fume hood for pre-digestion, evaporate the solution at 120°C until the yellow smoke dissipates, and add 1.0 mL HNO 3 , 4.0mL of water, screw on the lid and put it into a microwave digestion device for digestion according to the microwave digestion program. After the digestion is completed and cooled, open the digestion tank, evaporate the solution to 1mL at 120℃, transfer the sample to a clean polyethylene plastic bottle, wash the digestion tank 3-4 times with a small amount of distilled water, combine the washing liquid in a PET bottle, dilute and fix the volume to 50.0000g, and obtain the earth pit sauerkraut sample and the standard pickling pool sauerkraut sample, respectively.
[0030] In some embodiments, the microwave digestion program temperature rising conditions are: 1) Raise the temperature from room temperature to 100°C and keep it for 3 minutes; 2) Raise the temperature from 100°C to 120°C and keep it for 3 minutes; 3) Raise the temperature from 120°C to 150°C and keep it for 3 minutes; 4) Raise the temperature from 150°C to 170°C and hold for 3 minutes; 5) Raise the temperature from 170°C to 190°C and hold for 15 minutes.
[0031] It should be noted that the room temperature is 25°C.
[0032] S200, determining the inorganic elements in the earth pit sauerkraut sample and the standard pickling pool sauerkraut sample to determine the differential characteristic elements.
[0033] In some embodiments, the method for determining the inorganic elements is an inductively coupled plasma mass spectrometer analysis method.
[0034] In some embodiments, the working conditions of the inductively coupled plasma mass spectrometer analysis method include: ICP-MS analysis RF power 1350W, plasma gas flow rate 14L / min, auxiliary gas flow rate 1L / min, carrier gas flow rate 0.5L / min, integration time 0.1s, and mass number measurement points 3.
[0035] By measuring the inorganic elements in the earth pit pickled cabbage sample and the standard pickled cabbage sample, the difference characteristic elements can be determined through scientific quantitative analysis. In some embodiments, the difference characteristic elements include any one or more of aluminum, arsenic, boron, barium, beryllium, bismuth, cobalt, chromium, copper, gallium, germanium, lithium, manganese, molybdenum, niobium, nickel, lead, rubidium, antimony, selenium, tin, strontium, tellurium, titanium, thallium, vanadium, zinc, and zirconium.
[0036] In some embodiments, the differential characteristic elements include boron (B), barium (Ba), copper (Cu), lithium (Li), manganese (Mn), molybdenum (Mo), lead (Pb), rubidium (Rb), selenium (Se), strontium (Sr), titanium (Ti) and zinc (Zn).
[0037] S300, establishing a discrimination model between the earth pit sauerkraut and the standard pickling pool sauerkraut according to the content of the differential characteristic elements.
[0038] The analysis method used in the discriminant model is orthogonal partial least squares or classification discriminant analysis. For example, in some embodiments, SIMCA software can be used to perform orthogonal partial least squares discriminant analysis on earth pit pickled cabbage and standard pickled pool pickled cabbage, and the obtained orthogonal partial least squares discriminant model score diagram of earth pit pickled cabbage and standard pickled pool pickled cabbage shows that the discriminant analysis can 100% distinguish earth pit pickled cabbage from standard pickled pool pickled cabbage, so the orthogonal least squares discriminant analysis can more intuitively reflect the influence of different pickled cabbage pickling processes on the difference in characteristic element content.
[0039] In addition, in some embodiments, SPSS can be used to perform classification discriminant analysis to obtain Fisher's formula of the discriminant analysis model, which can also be used for subsequent automatic analysis and identification of unknown samples.
[0040] The method of establishing a discrimination model between the earth pit pickled cabbage and the standard pickled tank pickled cabbage according to the content of the differential characteristic elements comprises: According to the content M of the characteristic elements boron, barium, copper, lithium, manganese, molybdenum, lead, rubidium, selenium, strontium, titanium and zinc, Y can be obtained according to the discriminant model (1) to (2). 土坑酸菜 , Y 腌渍池酸菜 Value, the Y 土坑酸菜 , Y 腌渍池酸菜 The largest value is the origin of the corresponding sauerkraut sample. The discrimination models of earth pit sauerkraut and standard pickling pool sauerkraut are: Y土坑酸菜 =-1.3*M B +2.283*M Ba -2.32*M Cu +49.179*M Li +0.399*M Mn +31.276*M Mo +2.962*M Pb +4.076*M Rb +29.304*M Se +0.357*M Sr +3.228*M Ti +0.9*M Zn (1); Y 腌渍池酸菜 =9.045*M B -2.995*M Ba -5.504*M Cu +47.502*M Li +0.992*M Mn +47.023*M Mo -18.054*M Pb -0.004*M Rb +43.397*M Se +2.73*M Sr +0.435*M Ti -0.042*M Zn (2).
[0041] It should be noted that in the (1) to (2) discriminant models, M represents the content of each of the differential characteristic elements. The content can be obtained by an ICP-MS instrument detection method, and the unit of the content is μg / g. For example, in one embodiment, the differential characteristic elements are obtained by quantitative analysis of differential elements between earth pit sauerkraut and standard pickled pond sauerkraut. The information of the quantitative analysis of differential elements includes: units, element names, content of different samples and other information. The different content of each element represents that the element is different between different samples. By excluding some undetected elements or elements with small content differences between sauerkrauts (such as sample content fluctuations of 0.1 < ppm), the differential characteristic elements are obtained.
[0042] In some embodiments, the discriminant models (1) to (2) are obtained by the following method: SPSS software was used to conduct discriminant analysis on the contents of various elements in sauerkraut samples, and Fisher's discriminant classification functions were established for earth pit sauerkraut and standard pickling pool sauerkraut, respectively, thus obtaining the discriminant models (1) to (2) mentioned above.
[0043] It should be noted that the full name of SPSS software is Statistical Product and Service Solutions, or SPSS for short. The present invention can obtain the discriminant models (1) to (2) by substituting the differential characteristic element content data into the Fisher's discriminant function in the SPSS software.
[0044] S400, determining the content of the differential characteristic elements in the sauerkraut sample to be tested, and substituting the content of the differential characteristic elements in the sauerkraut sample to be tested into the discrimination model to distinguish the earth pit sauerkraut from the standard pickling pool sauerkraut. Example
[0045] 1. Sample collection 15 kinds of earth pit sauerkraut and 60 kinds of standard pickling pool sauerkraut from different origins were selected.
[0046] Sample preparation The whole earth pit pickled cabbage and standard pickled pool pickled cabbage were crushed, and 1.0000 g of uniform sample was added to the acid-boiled and cleaned PTFE (polytetrafluoroethylene) digestion tank, and 4.0 mL of HNO 3 , placed in a fume hood for pre-digestion, evaporate the solution at 120°C until the yellow smoke disappears, and add 1.0 mL HNO 3 , 4.0mL water, screw on the lid and put it into the microwave digestion device for digestion according to the microwave digestion program. After the digestion is completed and cooled, open the digestion tank, evaporate the solution to 1mL at 120℃, transfer the sample to a clean polyethylene plastic bottle, wash the digestion tank 3-4 times with a small amount of distilled water, combine the washing liquid in a PET bottle, dilute and fix the volume to 50.0000g, and obtain the earth pit sauerkraut sample and the standard pickling pool sauerkraut sample respectively.
[0047] Table 1 Microwave digestion program temperature settings step Temperature / ℃ Keep time min 1 100 3 2 120 3 3 150 3 4 170 3 5 190 15 3. Determination of inorganic elements in earth pit pickled cabbage and standard pickled cabbage, and identification of differential characteristic elements The sauerkraut sample after the sample pretreatment in step 2 was put on the machine to determine its inorganic elements.
[0048] The working conditions of the inductively coupled plasma mass spectrometer were set as follows: ICP-MS analysis radio frequency power 1350 W, plasma gas flow rate 14 L / min, auxiliary gas flow rate 1 L / min, carrier gas flow rate 0.5 L / min, integration time 0.1 s, and mass number measurement points 3.
[0049] Quantitative analysis of inorganic elements: The instrument intensity was calculated according to the dilution multiple to obtain the content of each element in the sauerkraut sample. The results of the contents of five types of earth pit sauerkraut and standard pickling pool sauerkraut were selected for illustration, and the results are shown in Table 2 below.
[0050] Table 2 Quantitative results of inorganic elements in sauerkraut samples from various earth pits and standard pickling pools Unit: μg / g As B Ba Be Bi Co Earth pit pickled cabbage-1 0.046 1.882263 2.29479 0 0.004 0.031 Earth pit pickled cabbage-2 0.054 1.18577 1.22518 0 0.002 0.037 Earth pit pickled cabbage-3 0.04 0.835249 1.22771 0 0.006 0.044 Earth pit pickled cabbage-4 0.049 2.260732 1.84874 0 0.006 0.047 Earth pit pickled cabbage-5 0.048 2.366911 1.94234 0 0.011 0.021 Standard pickling pool sauerkraut - 1 0.047 3.32456 1.23545 0.001 0.011 0.02 Standard pickling pool sauerkraut - 2 0.048 2.15741 0.999575 0.001 0.01 0.018 Standard pickling pool sauerkraut -3 0.054 2.81358 1.2834 0.003 0.011 0.02 Standard pickling pool sauerkraut - 4 0.053 2.13145 1.0198 0.001 0.007 0.012 Standard pickling pool sauerkraut -5 0.051 3.52132 1.65891 0.001 0.007 0.012 Unit: μg / g Cr Cu Ga Ge Li Mn Earth pit pickled cabbage-1 0.444 0.70244 0.106 0.001 0.170894 1.74276 Earth pit pickled cabbage-2 0.48 0.645724 0.135 0.002 0.12586 1.52627 Earth pit pickled cabbage-3 0.44 0.477502 0.186 0.003 0.13446 1.6443 Earth pit pickled cabbage-4 0.431 0.677326 0.186 0.002 0.13455 2.42029 Earth pit pickled cabbage-5 0.415 0.45594 0.194 0.001 0.11272 2.01609 Standard pickling pool sauerkraut - 1 0.405 0.595647 0.189 0.001 0.142079 4.23097 Standard pickling pool sauerkraut - 2 0.428 0.422064 0.183 0 0.116514 3.89227 Standard pickling pool sauerkraut -3 0.431 0.34394 0.193 0.001 0.183566 4.69731 Standard pickling pool sauerkraut - 4 0.383 0.847538 0.192 0 0.109686 3.89116 Standard pickling pool sauerkraut -5 0.455 0.580106 0.2 0.001 0.19279 4.70147 Unit: μg / g Mo Nb Ni Pb R Sb Earth pit pickled cabbage-1 0.127214 0.008 0.112 0.066893 2.84865 0.004 Earth pit pickled cabbage-2 0.146002 0.008 0.11 0.051979 2.78921 0.003 Earth pit pickled cabbage-3 0.154291 0.012 0.09 0.126459 2.76012 0.004 Earth pit pickled cabbage-4 0.165974 0.011 0.105 0.440827 4.23782 0.004 Earth pit pickled cabbage-5 0.109565 0.003 0.096 0.073415 3.98357 0.004 Standard pickling pool sauerkraut - 1 0.065497 0.003 0.054 0.140559 2.50053 0.004 Standard pickling pool sauerkraut - 2 0.061832 0.001 0.027 0.125713 2.57956 0.003 Standard pickling pool sauerkraut -3 0.055001 0.003 0.03 0.176488 3.15796 0.003 Standard pickling pool sauerkraut - 4 0.056713 0.003 0.03 0.136064 2.35057 0.003 Standard pickling pool sauerkraut -5 0.071483 0.007 0.034 0.226134 2.95658 0.003 Unit: μg / g Se Sn Sr Te Ti Tl Earth pit pickled cabbage-1 0.340411 0.364 6.37962 ND 1.844 0.002 Earth pit pickled cabbage-2 0.392551 0.37 3.75994 ND 2.04644 0.002 Earth pit pickled cabbage-3 0.402301 0.278 3.74958 ND 2.17563 0.003 Earth pit pickled cabbage-4 0.363495 0.26 5.86629 ND 2.95684 0.003 Earth pit pickled cabbage-5 0.32789 0.336 5.64168 ND 2.32193 0.002 Standard pickling pool sauerkraut - 1 0.404897 0.391 11.3988 ND 2.52639 0.002 Standard pickling pool sauerkraut - 2 0.456918 0.355 10.3283 ND 3.05071 0.002 Standard pickling pool sauerkraut -3 0.257263 0.339 8.42308 ND 3.59126 0.002 Standard pickling pool sauerkraut - 4 0.40721 0.373 9.3754 ND 2.0013 0.002 Standard pickling pool sauerkraut -5 0.516395 0.385 13.5112 ND 3.79029 0.002 Unit: μg / g V Zn Zr Earth pit pickled cabbage-1 0.112 2.01079 0.035 Earth pit pickled cabbage-2 0.125 1.17937 0.052 Earth pit pickled cabbage-3 0.085 1.16103 0.07 Earth pit pickled cabbage-4 0.083 2.69404 0.068 Earth pit pickled cabbage-5 0.088 2.32866 0.03 Standard pickling pool sauerkraut - 1 0.099 3.64493 0.043 Standard pickling pool sauerkraut - 2 0.103 2.58711 0.017 Standard pickling pool sauerkraut -3 0.102 2.64575 0.016 Standard pickling pool sauerkraut - 4 0.15 3.1038 0.015 Standard pickling pool sauerkraut -5 0.164 3.45464 0.016 It should be noted that the information of the quantitative analysis of the differential elements between earth pit pickled cabbage and standard pickled pool pickled cabbage includes: unit, element name, content of different samples, etc. The different content of each element represents that there are differences between different samples. According to the results, it is known through analysis that some undetectable elements or elements with small content differences between pickled cabbages (sample content fluctuates up and down 0.1 < ppm) are excluded, and the differential characteristic elements are obtained. The content of differential characteristic elements is shown in Table 3.
[0051] Table 3 The content of different characteristic elements between earth pit pickled cabbage and standard pickled cabbage Unit: μg / g B Ba Cu Li Mn Mo Earth pit pickled cabbage-1 1.882263 2.29479 0.70244 0.170894 1.74276 0.127214 Earth pit pickled cabbage-2 1.18577 1.22518 0.645724 0.12586 1.52627 0.146002 Earth pit pickled cabbage-3 0.835249 1.22771 0.477502 0.13446 1.6443 0.154291 Earth pit pickled cabbage-4 2.260732 1.84874 0.677326 0.13455 2.42029 0.165974 Earth pit pickled cabbage-5 2.366911 1.94234 0.45594 0.11272 2.01609 0.109565 Standard pickling pool sauerkraut - 1 3.32456 1.23545 0.595647 0.142079 4.23097 0.065497 Standard pickling pool sauerkraut - 2 2.15741 0.999575 0.422064 0.116514 3.89227 0.061832 Standard pickling pool sauerkraut -3 2.81358 1.2834 0.34394 0.183566 4.69731 0.055001 Standard pickling pool sauerkraut - 4 2.13145 1.0198 0.847538 0.109686 3.89116 0.056713 Standard pickling pool sauerkraut -5 3.52132 1.65891 0.580106 0.19279 4.70147 0.071483 Unit: μg / g Pb R Se Sr Ti Zn Earth pit pickled cabbage-1 0.066893 2.84865 0.340411 6.37962 1.844 2.01079 Earth pit pickled cabbage-2 0.051979 2.78921 0.392551 3.75994 2.04644 1.17937 Earth pit pickled cabbage-3 0.126459 2.76012 0.402301 3.74958 2.17563 1.16103 Earth pit pickled cabbage-4 0.440827 4.23782 0.363495 5.86629 2.95684 2.69404 Earth pit pickled cabbage-5 0.073415 3.98357 0.32789 5.64168 2.32193 2.32866 Standard pickling pool sauerkraut - 1 0.140559 2.50053 0.404897 11.3988 2.52639 3.64493 Standard pickling pool sauerkraut - 2 0.125713 2.57956 0.456918 10.3283 3.05071 2.58711 Standard pickling pool sauerkraut -3 0.176488 3.15796 0.257263 8.42308 3.59126 2.64575 Standard pickling pool sauerkraut - 4 0.136064 2.35057 0.40721 9.3754 2.0013 3.1038 Standard pickling pool sauerkraut -5 0.226134 2.95658 0.516395 13.5112 3.79029 3.45464 4. Establishment of discriminant model According to the information of the content of each characteristic element in sauerkraut from known origins, the orthogonal partial least squares discriminant model and classification discriminant model of earth pit sauerkraut and pickling pond sauerkraut were established by using SIMCA and SPSS, respectively.
[0052] (1) Orthogonal partial least squares discriminant model Figure 2 This is a score diagram of the orthogonal partial least squares discriminant model of earth pit pickled cabbage and standard pickled tank pickled cabbage obtained in the embodiment of the present invention. Figure 2 As shown in the figure, SIMCA software was used to perform orthogonal partial least squares discriminant analysis on earth pit sauerkraut and standard pickling pool sauerkraut. The green group A was standard pickling pool sauerkraut, and the blue group B was earth pit sauerkraut. The scatter plot can 100% distinguish earth pit sauerkraut from standard pickling pool sauerkraut. Therefore, the least squares discriminant analysis can more intuitively reflect the impact of different sauerkraut pickling processes on the differences in characteristic element contents.
[0053] (2) Classification and discrimination model The known types of sauerkraut samples that have undergone orthogonal partial least squares discriminant analysis are imported into the discriminant analysis database of SPSS to create a discriminant analysis model, which can be used for the automatic analysis and identification of subsequent unknown samples.
[0054] Fisher's discriminant formula can be obtained through the classification discriminant analysis model. According to the content M of the difference characteristic elements B, Ba, Cu, Li, Mn, Mo, Pb, Rb, Se, Sr, Ti and Zn, Y can be obtained according to the discriminant formulas (1) to (2). 土坑酸菜 , Y 腌渍池酸菜 Value, Y 土坑酸菜 , Y 腌渍池酸菜The largest value is the origin of the corresponding sauerkraut sample. The discrimination models of earth pit sauerkraut and standard pickling pool sauerkraut are: Y 土坑酸菜 =-1.3*M B +2.283*M Ba -2.32*M Cu +49.179*M Li +0.399*M Mn +31.276*M Mo +2.962*M Pb +4.076*M Rb +29.304*M Se +0.357*M Sr +3.228*M Ti +0.9*M Zn (1); Y 腌渍池酸菜 =9.045*M B -2.995*M Ba -5.504*M Cu +47.502*M Li +0.992*M Mn +47.023*M Mo -18.054*M Pb -0.004*M Rb +43.397*M Se +2.73*M Sr +0.435*M Ti -0.042*M Zn (2).
[0055] 5. Unknown sample identification Ten unknown types of pickled cabbage were selected as blind samples for identification, and the results were obtained by using orthogonal partial least squares discriminant analysis, as shown in the figure. Figure 3 The orthogonal partial least squares discriminant model score diagram of 10 unknown samples and pickled pool and earth pit sauerkraut from various origins in the embodiment of the present invention is shown. The brown samples s1 to s10 are blind samples and are divided into two parts. The dotted line is closest to the green earth pit sauerkraut and is identified as earth pit sauerkraut, and the solid line is close to the pickled pool sauerkraut from various origins and is identified as pickled pool sauerkraut.
[0056] At the same time, SPSS was used for classification and discriminant analysis, such as Figure 4 The SPSS classification discriminant analysis results in the embodiment of the present invention are shown in Figure 1. Classification 1 is earth pit pickled cabbage, and classification 2 is pickled pool pickled cabbage. Ten raw pickled cabbage blind samples were discriminated and analyzed, and the accuracy rate reached 80%. Among them, two pickled pool pickled cabbage samples were misclassified as earth pit pickled cabbage.
[0057] Therefore, the identification method of the present invention can accurately identify earth pit sauerkraut from different origins and standard pickling pool sauerkraut, has a wide range of operational feasibility, and is of great significance for standardizing the sauerkraut market.
[0058] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the scope defined by the claims.
Claims
1. A method for distinguishing earth pit pickled cabbage from standard pickled cabbage, characterized in that: include: Obtain known earth pit sauerkraut samples and standard pickling pool sauerkraut samples from different origins; Determine the inorganic elements in the earth pit sauerkraut sample and the standard pickling pool sauerkraut sample to determine the differential characteristic elements; Establishing a discrimination model between the earth pit pickled cabbage and the standard pickled tank pickled cabbage according to the content of the differential characteristic elements; The contents of the differential characteristic elements in the sauerkraut samples to be tested are determined, and the contents of the differential characteristic elements in the sauerkraut samples to be tested are substituted into the discrimination model to distinguish between earth pit sauerkraut and standard pickling pool sauerkraut.
2. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage according to claim 1, characterized in that: The differential characteristic elements include any one or more of aluminum, arsenic, boron, barium, beryllium, bismuth, cobalt, chromium, copper, gallium, germanium, lithium, manganese, molybdenum, niobium, nickel, lead, rubidium, antimony, selenium, tin, strontium, tellurium, titanium, thallium, vanadium, zinc, and zirconium.
3. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage according to claim 2, characterized in that: The differential characteristic elements include boron, barium, copper, lithium, manganese, molybdenum, lead, rubidium, selenium, strontium, titanium and zinc.
4. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage according to claim 1, characterized in that: The analysis method adopted by the discriminant model is orthogonal partial least squares method or classification discriminant analysis.
5. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage according to claim 3, characterized in that: The method of establishing a discrimination model between the earth pit pickled cabbage and the standard pickled tank pickled cabbage according to the content of the differential characteristic elements comprises: According to the content M of the characteristic elements of boron, barium, copper, lithium, manganese, molybdenum, lead, rubidium, selenium, strontium, titanium and zinc, Y can be obtained according to the discrimination model (1) to (2) 土坑酸菜 , Y 腌渍池酸菜 Value, the Y 土坑酸菜 , Y 腌渍池酸菜 The largest value is the origin of the corresponding sauerkraut sample. The discrimination models of earth pit sauerkraut and standard pickling pool sauerkraut are: Y 土坑酸菜 =-1.3*M B +2.283*M Ba -2.32*M Cu +49.179*M Li +0.399*M Mn +31.276*M M o +2.962*M Pb +4.076*M Rb +29.304*M Se +0.357*M Sr +3.228*M Ti +0.9*M Zn (1); Y 腌渍池酸菜 =9.045*M B -2.995*M Ba -5.504*M Cu +47.502*M Li +0.992*M Mn +47.023* M Mo -18.054*M Pb -0.004*M Rb +43.397*M Se +2.73*M Sr +0.435*M Ti -0.042*M Zn (2)。 6. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage according to claim 5, characterized in that: The discriminant models (1) to (2) are obtained by the following method: SPSS software was used to perform discriminant analysis on the contents of various elements in the sauerkraut samples, and Fisher's discriminant classification functions were established for the earth pit sauerkraut and the standard pickling pool sauerkraut, respectively, thus obtaining the discriminant models (1) to (2) described above.
7. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage according to claim 1, characterized in that: The method of obtaining known earth pit sauerkraut samples and standard pickling pool sauerkraut samples from different origins comprises: collecting earth pit sauerkraut and standard pickling pool sauerkraut from multiple origins, chopping whole earth pit sauerkraut and standard pickling pool sauerkraut into pieces and mixing them evenly to obtain uniform earth pit sauerkraut and uniform standard pickling pool sauerkraut respectively; 1.0000 g of uniform earth pit sauerkraut and uniform standard pickled pool sauerkraut were respectively added to a polytetrafluoroethylene digestion tank, 4.0 mL of HNO3 was added, and the tank was placed in a fume hood for pre-digestion. The solution was evaporated at 120°C until the yellow smoke was gone, 1.0 mL of HNO3 and 4.0 mL of water were added, the lid was screwed on, and the tank was placed in a microwave digestion device for digestion according to the microwave digestion procedure. After the digestion was completed and cooled, the digestion tank was opened, and the solution was evaporated to 1 mL at 120°C. The sample was transferred to a clean polyethylene plastic bottle, the digestion tank was washed 3-4 times with a small amount of distilled water, the washing liquid was combined in a PET bottle, and the volume was diluted to 50.0000 g to obtain the earth pit sauerkraut sample and the standard pickled pool sauerkraut sample, respectively.
8. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage according to claim 7, characterized in that: The microwave digestion program temperature rising conditions are: 1) Raise the temperature from room temperature to 100°C and keep it for 3 minutes; 2) Raise the temperature from 100°C to 120°C and keep it for 3 minutes; 3) Raise the temperature from 120°C to 150°C and keep it for 3 minutes; 4) Raise the temperature from 150°C to 170°C and hold for 3 minutes; 5) Raise the temperature from 170°C to 190°C and hold for 15 minutes.
9. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage according to claim 1, characterized in that: The method for determining the inorganic elements is an inductively coupled plasma mass spectrometer analysis method.
10. The method for distinguishing earth pit pickled cabbage from standard pickled cabbage according to claim 9, characterized in that: The working conditions of the inductively coupled plasma mass spectrometer analysis method include: The radio frequency power of ICP-MS analysis was 1350 W, the plasma gas flow rate was 14 L / min, the auxiliary gas flow rate was 1 L / min, the carrier gas flow rate was 0.5 L / min, the integration time was 0.1 s, and the number of mass number measurement points was 3.